Alkylcyanation of Unactivated Alkenes with Protic C(sp3)‐H Feedstocks via Radical‐Initiated Intramolecular Cyano Group Migration Enabled by Photoredox/Brønsted Base Dual Catalysis DOI
Yang Hong, Hong‐Ping Deng

ChemPhotoChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract Cyanofunctionalization of alkenes via radical‐initiated cyano migration was a straightforward pathway to access alkyl nitriles. Herein, By the synergistic merger photoredox catalysis and Brønsted base catalysis, mild protocol alkylcyanation unactivated with protic C(sp 3 )−H feedstocks intramolecular 1,4‐cyano group reported. This method enabled in an atom‐, step‐economy manner, delivering series γ‐cyanoester derivatives moderate excellent yields.

Language: Английский

Copper-Catalyzed Radical Relay 1,3-Carbocarbonylation across Two Distinct C═C Bonds DOI

Nan‐Nan Dai,

Yue-Jiao Lu,

Zhong-Qi Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3014 - 3019

Published: March 28, 2024

The radical relay provides an effective paradigm for intermolecular assembly to achieve functionalization across remote chemical bonds. Herein, we report the first 1,3-carbocarbonylation of α-carbonyl alkyl bromides two separate C═C reaction is highly chemo- and regioselective, with C(sp3)–C(sp3) bonds one C═O bond formed in a single orchestrated operation. In addition, synthesis method under mild conditions using inexpensive copper as catalyst allows facile access structurally diverse products. plausible mechanism investigated through series control experiments, including trapping, clock critical intermediate 18O labeling experiment.

Language: Английский

Citations

12
Pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition for the synthesis of pyridine isosteres DOI
Yuan Liu,

Shuang Lin,

Zhengwei Ding

et al.

Chem, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 1, 2024

Language: Английский

Citations

11
Divergent Enantioselective Access to Diverse Chiral Compounds from Bicyclo[1.1.0]butanes and α,β-Unsaturated Ketones under Catalyst Control DOI
Jinwook Jeong, Shi Cao, Hyung‐Joon Kang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 30, 2024

Achieving structural and stereogenic diversity from the same starting materials remains a fundamental challenge in organic synthesis, requiring precise control over selectivity. Here, we report divergent catalytic methods that selectively yield either cycloaddition or addition/elimination products bicyclo[1.1.0]butanes α,β-unsaturated ketones. By employing chiral Lewis acid Brønsted catalysts, achieved excellent regio-, diastereo-, enantioselectivity across all three distinct transformations, affording diverse array of synthetically valuable bicyclo[2.1.1]hexanes cyclobutenes. The outcomes are controlled by differential activation substrates specific catalyst with reaction conditions dictating pathway This strategy demonstrates power catalysis creating molecular complexity diversity, offering tool for synthesis enantioenriched building blocks.

Language: Английский

Citations

11
Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches DOI
Yanli Yin,

Mengdi You,

Xiangtao Li

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The use of olefins in the construction cyclic compounds represents a powerful strategy for advancing pharmaceutical industry.

Language: Английский

Citations

1
Photoredox/nickel dual-catalysis-enabled synthesis of N-heterocycles from alkyl chlorides and alkenes DOI

Xuege Yang,

Lou Shi, Ruoyu Qin

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 553, P. 113806 - 113806

Published: Jan. 1, 2024

Language: Английский

Citations

6
Pyridine-Boryl Radical-Catalyzed [3π + 2σ] Cycloaddition for the Synthesis of Pyridine Bioisosteres DOI Creative Commons
Honggen Wang, Yuan Liu,

Shuang Lin

et al.

Published: April 1, 2024

The exploration of C(sp3)-rich three-dimensional (3D) scaffolds as bioisosteres for planar aromatics has garnered increasing attention. While the bioisosterism benzenes been extensively studied, pyridines, second most prevalent aromatic compounds in pharmaceuticals, faces additional challenges and encountered surprisingly limited success. In this study, we propose unprecedented 2-azabicyclo[3.1.1]heptenes effective 1,3,5-trisubstituted pyridines terms not only 3D conformation but also basicity. We develop a pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition reaction vinyl azides with bicyclo[1.1.0]butanes (BCBs) an efficient synthetic approach. Synthetic manipulation products reveals valuable handles, allowing modular synthesis various pyridine bioisosteres.

Language: Английский

Citations

6
SO2-Insertion induced enantioselective oxysulfonylation to access β-chiral sulfones with quaternary carbon stereocenters DOI
Jun Zhang,

Xuefeng Wang,

Peiqi Wang

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(3), P. 908 - 913

Published: Dec. 5, 2023

Language: Английский

Citations

11
Redox-Neutral Cyclization of 2-Isocyanobiaryls through Photoredox/PPh3 Dual Catalysis DOI
Xiaoting Wu, Pu Chen,

Mengran Gan

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(51), P. 9186 - 9190

Published: Dec. 15, 2023

The photoredox/PPh3-mediated cyclization of 2-isocyanobiaryls has been developed. A substantial range functional-group-rich phenanthridine derivatives were synthesized at room temperature in a highly selective and atom-economic manner. Mechanistic studies suggested that the process is probably mediated both by Ph3P radical cation with key 1,2-hydride transfer hydrogen atom generated through O–H bond homolytic cleavage Ph3P–OH intermediate.

Language: Английский

Citations

11
Synthesis of Acylbenzo[b]thiophenes, Benzofurans and Indoles via Intramolecular Oxidative Cyclization Enabled by Photocatalytic Hydrogen Atom Transfer (HAT) DOI Creative Commons

Fen-Dou Wang,

Jin Jiang,

Tiantian Xu

et al.

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100119 - 100119

Published: Jan. 1, 2025

An efficient strategy for intramolecular oxidative cyclization of 2-alkynylthioanisoles toward 3-acylbenzo[b]thiophenes by photochemical hydrogen atom transfer catalysis has been developed. 3-Acylbenzo[b]selenophenes, benzofurans and indoles can also be prepared this protocol. This reaction is convenient to perform at room temperature under simple conditions using air as the oxidant. Mechanistic studies revealed that formation α-thioalkyl radicals intermediate crucial.Graphical abstract

Language: Английский

Citations

0
Chiral ruthenium complex/Ph 2 P(2-furyl)–catalyzed asymmetric nucleophilic addition of aryl aldehyde hydrazones to simple ketones DOI Creative Commons

Chenghao Zhu,

Zihao Ye, Haining Wang

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(12)

Published: March 21, 2025

An efficient synthesis of chiral tertiary alcohols through asymmetric nucleophilic addition reaction aldehyde hydrazones to simple ketones (especially aryl/methyl ketones) has been well established. Aryl aldehydes could be used as latent benzyl carbanion equivalents via reductive polarity reversal. The key the success was combination an achiral monophosphine ligand Ph 2 P(2-furyl) with a diamine derivative, which enhanced enantioselectivity and reactivity. Density functional theory calculations revealed hydrogen bond interactions between ligand, base anion, combined induce desired enantioselectivity. Moreover, further synthetic transformation high chirality transfer also demonstrated.

Language: Английский

Citations

0